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Hydrothermal reaction of Ge and Se with Ag(CH 3 COO) in the presence of alkali metal carbonates affords the open framework selenidogermanates(IV) A 3 [AgGe 4 Se 10 ]·2H 2 O (A = Rb, Cs), 1 and 2, which contain corner linked adamantane-like Ge 4 Se 10  cages and AgSe 4  tetrahedra. The analogous reaction with Mn(CH 3 COO) 2  yields the isostructural tetragonal compounds A 2 [MnGe 4 Se 10 ]·3H 2 O (A = Rb, Cs), 3 and 4. The cations are sited at a general position in the channels of the silver bridged anionic framework of 1 and 2 and exhibit a disordered pattern of occupation (s.o.f. = 0.75) with one of the two crystallographically independent water oxygen atoms O(2) (s.o.f. = 0.25). In contrast, the Rb +  cations in 3 are disordered over all three cation/oxygen sites, and the cation/water occupation pattern is fully reversed for the larger Cs +  cations in 4 in comparison to 1 and 2.

Quaternary Selenidogermanates(IV) A 3 [AgGe 4 Se 10 ]·2H 2 O and A 2 [MnGe 4 Se 10 ]·3H 2 O (A = Rb, Cs) with Open Framework Structures